Method of forming a structure on a substrate

ABSTRACT

The invention relates to depositing a layer on a substrate in a reactor, by:
         introducing a first precursor comprising a silicon halide in the reactor;   introducing a second precursor in the reactor;   providing an energy source to create a plasma from the second precursor so that the second precursor reacts with the first precursor until a primary layer comprising silicon and second precursor of a desired thickness is formed;   stop introducing the second precursor; and,   subsequently introducing the silicon halide in the reactor at a temperature causing decomposition of the silicon halide precursor to provide a substantially pure amorphous silicon layer on top of the primary layer.

FIELD OF INVENTION

The present disclosure generally relates to methods and systems for manufacturing electronic devices. More particularly, the disclosure relates to methods for providing a structure by depositing a layer on a substrate in a reactor.

BACKGROUND

As the trend has pushed structures in semiconductor devices to smaller and smaller sizes, different patterning techniques have arisen to produce these structures. These techniques include spacer defined double or quadruple patterning, (immersion) lithography (193i), extreme ultraviolet lithography (EUV), and directed self-assembly (DSA) lithography. Lithography may be combined with spacer defined double or quadruple patterning.

In these techniques it may be advantageous to transfer the pattern of the polymer resist to a hardmask. A hardmask is a material used in semiconductor processing as an etch mask with a good etching resistance and etching selectivity to produce small structures.

Spacers are also widely used in semiconductor manufacturing to protect against subsequent processing steps. For example, silicon nitride spacers formed beside gate electrodes can be used as a mask to protect underlying source/drain areas during doping or implanting steps. As the physical geometry of structures of semiconductor devices shrinks, the gate electrode spacer becomes smaller and smaller. The spacer width is limited by the silicon nitride thickness that can be deposited conformably over the dense gate electrodes lines with a plasma enhanced atomic layer deposition (PEALD) or chemical vapor deposition (PECVD) process.

Hardmasks or spacers produced by current PEALD or PECVD silicon nitride processes may have a wet etch rate which may be too high. It is therefore advantageous to produce a layer for a hardmask or a spacer with a higher etching resistance and etching selectivity. As a result, a layer with advanced properties may be required.

SUMMARY

In accordance with at least one embodiment of the invention there is provided a method of providing a structure by depositing a layer on a substrate in a reactor, the method comprising:

introducing a first precursor comprising a silicon halide in the reactor;

introducing a second precursor in the reactor;

providing an energy source to create a plasma from the second precursor so that the second precursor reacts with the first precursor until a primary layer comprising silicon and second precursor of a desired thickness is formed;

stop introducing the second precursor; and,

subsequently introducing the silicon halide in the reactor at a temperature causing decomposition of the silicon halide precursor to provide a substantially pure amorphous silicon layer on top of the primary layer. The layer comprising the primary layer comprising silicon and second precursor and a substantially pure amorphous silicon layer on top may have a an improved etch rate in hydro fluoride HF. The layer may be easily deposited because no different first precursor is required for the primary and the substantially pure amorphous layer. Further no different tool nor any transfer to a different reaction chamber may be necessary. The substantially pure amorphous silicon layer may be selectively deposited on the primary layer such that it is only deposited on top of this layer and not on other layers. It may also be deposited on the complete surface.

According to a further embodiment there is provided a method of providing a structure by depositing a layer on a substrate in a reactor, the method comprising:

introducing a first precursor comprising silicon halide in the reactor at a temperature causing decomposition of the silicon halide precursor to provide a substantially pure amorphous silicon,

subsequently introducing a second precursor in the reactor; and,

providing an energy source to create a plasma from the second precursor so that the second precursor reacts with the first precursor until a primary layer comprising silicon and second precursor of a desired thickness is formed.

The layer comprising the substantially pure amorphous silicon layer and the primary layer comprising silicon and second precursor on top may have a an improved etch rate. The pure amorphous silicon layer may protect an underlying layer from the second precursor which may be advantageous.

For purposes of summarizing the invention and the advantages achieved over the prior art, certain objects and advantages of the invention have been described herein above. Of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught or suggested herein without necessarily achieving other objects or advantages as may be taught or suggested herein.

All of these embodiments are intended to be within the scope of the invention herein disclosed. These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of certain embodiments having reference to the attached figures, the invention not being limited to any particular embodiment(s) disclosed.

BRIEF DESCRIPTION OF THE FIGURES

These and other features, aspects, and advantages of the invention disclosed herein are described below with reference to the drawings of certain embodiments, which are intended to illustrate and not to limit the invention.

FIG. 1 is a flowchart in accordance with at least one embodiment of the invention.

FIGS. 2A-2B show images from layers deposited according to an embodiment on some high aspect ratio structures.

It may be appreciated that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale to help improve understanding of illustrated embodiments of the present disclosure.

DETAILED DESCRIPTION

Although certain embodiments and examples are disclosed below, it will be understood by those in the art that the invention extends beyond the specifically disclosed embodiments and/or uses of the invention and obvious modifications and equivalents thereof. Thus, it is intended that the scope of the invention disclosed should not be limited by the particular disclosed embodiments described below.

The particular implementations shown and described are illustrative of the invention and its best mode and are not intended to otherwise limit the scope of the aspects and implementations in any way. Indeed, for the sake of brevity, conventional manufacturing, connection, preparation, and other functional aspects of the system may not be described in detail.

The primary layer may be a silicon nitride film which may have a wide variety of applications, as will be apparent to the skilled artisan, such as in planar logic, DRAM, and NAND Flash devices. More specifically, conformal silicon nitride thin films that display uniform etch behavior have a wide variety of applications, both in the semiconductor industry and also outside of the semiconductor industry.

According to some embodiments of the present disclosure, various silicon nitride films and precursors and methods for depositing those films by atomic layer deposition (ALD) are provided. Importantly, in some embodiments the silicon nitride films have a relatively uniform etch rate for both the vertical and the horizontal portions, when deposited onto 3-dimensional structures. Such three-dimensional structures may include, for example and without limitation, FinFETS or other types of multiple gate FETs.

Thin film layers comprising silicon nitride can be deposited by plasma-enhanced atomic layer deposition (PEALD) or chemical vapor deposition (PECVD) type processes or by thermal ALD processes. In some embodiments a silicon nitride thin film is deposited over a three dimensional structure, such as a fin in the formation of a finFET device, and/or in the application of spacer defined double patterning (SDDP) and/or spacer defined quadruple patterning (SDQP). In some embodiments a silicon nitride thin film is deposited over a flat layer as a hard mask and subsequent layer are positioned on top for lithographic processing.

The formula of the silicon nitride is generally referred to herein as SiN for convenience and simplicity. However, the skilled artisan will understand that the actual formula of the silicon nitride, representing the Si:N ratio in the film and excluding hydrogen or other impurities, can be represented as SiNx, where x varies from about 0.5 to about 2.0, as long as some Si—N bonds are formed. In some cases, x may vary from about 0.9 to about 1.7, from about 1.0 to about 1.5, or from about 1.2 to about 1.4. In some embodiments silicon nitride is formed where Si has an oxidation state of +IV and the amount of nitride in the material might vary.

ALD-type processes are based on controlled, generally self-limiting surface reactions. Gas phase reactions are typically avoided by contacting the substrate alternately and sequentially with the precursors. Vapor phase precursors are separated from each other in the reaction chamber, for example, by removing excess precursors and/or reaction byproducts between precursor pulses. The precursors may be removed from proximity with the substrate surface with the aid of a purge gas and/or vacuum. In some embodiments excess precursors and/or reaction byproducts are removed from the reaction space by purging, for example with an inert gas.

The methods presented herein provide for deposition of SiN thin films on substrate surfaces. Geometrically challenging applications are also possible due to the nature of ALD-type processes. According to some embodiments, ALD-type processes are used to form SiN thin films on substrates such as integrated circuit workpieces, and in some embodiments on three-dimensional structures on the substrates. In some embodiments, ALD type processes comprise alternate and sequential contact of the substrate with a silicon precursor and a nitrogen precursor. In some embodiments, a silicon precursor contacts the substrate such silicon species adsorb onto the surface of the substrate. In some embodiments, the silicon species may be same as the silicon precursor, or may be modified in the adsorbing step, such as by losing one or more ligands.

According to certain embodiments, a silicon nitride thin film may be formed on a substrate by an ALD-type process comprising multiple silicon nitride deposition cycles, each silicon nitride deposition cycle comprising:

(1) contacting a substrate with a first silicon precursor such that silicon species adsorb on the substrate surface;

(2) contacting the substrate with a nitrogen precursor; and

(3) repeating steps (1) and (2) as many times as required to achieve a thin film of a desired thickness and composition. Excess precursors may be removed from the vicinity of the substrate, for example by purging from the reaction space with an inert gas, after each contacting step.

PEALD Processes

In some embodiments, plasma enhanced ALD (PEALD) processes are used to deposit SiN layers. Briefly, a substrate or workpiece is placed in a reaction chamber and subjected to alternately repeated surface reactions. In some embodiments, thin SiN films are formed by repetition of a self-limiting ALD cycle. Preferably, for forming SiN films, each ALD cycle comprises at least two distinct phases. The provision and removal of a precursor from the reaction space may be considered a phase. In a first phase, a first precursor comprising silicon is provided and forms no more than about one monolayer on the substrate surface. This precursor is also referred to herein as “the silicon precursor,” “silicon-containing precursor,” “silicon halide”, or “silicon reactant” and may be, for example, H₂SiI₂.

In a second phase, a second precursor comprising a reactive species is provided and may convert adsorbed silicon species to silicon nitride. In some embodiments the second precursor comprises a nitrogen precursor. In some embodiments, the reactive species comprises an excited species. In some embodiments the second precursor comprises a species from a nitrogen containing plasma. In some embodiments, the second precursor comprises nitrogen radicals, nitrogen atoms and/or nitrogen plasma. In some embodiments, the second precursor may comprise N-containing plasma or a plasma comprising N. In some embodiments, the second precursor may comprise a plasma comprising N-containing species. In some embodiments the second precursor may comprise nitrogen atoms and/or N* radicals. The second precursor may comprise other species that are not nitrogen precursors. In some embodiments, the second precursor may comprise a plasma of hydrogen, radicals of hydrogen, or atomic hydrogen in one form or another. In some embodiments, the second precursor may comprise a species from a noble gas, such as He, Ne, Ar, Kr, or Xe, preferably Ar or He, for example as radicals, in plasma form, or in elemental form. These reactive species from noble gases do not necessarily contribute material to the deposited film, but can in some circumstances contribute to film growth as well as help in the formation and ignition of plasma. In some embodiments a gas that is used to form a plasma may flow constantly throughout the deposition process but only be activated intermittently. In some embodiments, the second precursor does not comprise a species from a noble gas, such as Ar. Thus, in some embodiments the adsorbed silicon precursor is not contacted with a reactive species generated by a plasma from Ar

Additional phases may be added and phases may be removed as desired to adjust the composition of the final film.

One or more of the precursors may be provided with the aid of a carrier gas, such as Ar or He. In some embodiments the first precursor and the second precursor are provided with the aid of a carrier gas.

In some embodiments, two of the phases may overlap, or be combined. For example, the silicon precursor and the second precursor may be provided simultaneously in pulses that partially or completely overlap. In addition, although referred to as the first and second phases, and the first and second precursors, the order of the phases may be varied, and an ALD cycle may begin with any one of the phases. That is, unless specified otherwise, the precursors can be provided in any order, and the process may begin with any of the precursors.

As discussed in more detail below, in some embodiments for depositing a silicon nitride film, one or more deposition cycles begin with provision of the silicon precursor, followed by the second precursor. In other embodiments deposition may begin with provision of the second precursor, followed by the silicon precursor.

In some embodiments the substrate on which deposition is desired, such as a semiconductor workpiece, is loaded into a reactor. The reactor may be part of a cluster tool in which a variety of different processes in the formation of an integrated circuit are carried out. In some embodiments a flow-type reactor is utilized. In some embodiments a shower head type of reactor is utilized. In some embodiments, a space divided reactor is utilized. In some embodiments a high-volume manufacturing-capable single wafer ALD reactor is used. In other embodiments a batch reactor comprising multiple substrates is used. For embodiments in which batch ALD reactors are used, the number of substrates is preferably in the range of 10 to 200, more preferably in the range of 50 to 150, and most preferably in the range of 100 to 130.

Exemplary single wafer reactors, designed specifically to enhance ALD processes, are commercially available from ASM America, Inc. (Phoenix, Ariz.) under the tradenames Pulsar® 2000 and Pulsar® 3000 and ASM Japan K.K (Tokyo, Japan) under the tradename Eagle® XP, XP8 and Dragon®. Exemplary batch ALD reactors, designed specifically to enhance ALD processes, are commercially available from and ASM Europe B.V (Almere, Netherlands) under the tradenames A400™ and A412™.

In some embodiments, if necessary, the exposed surfaces of the workpiece can be pretreated to provide reactive sites to react with the first phase of the ALD process. In some embodiments a separate pretreatment step is not required. In some embodiments the substrate is pretreated to provide a desired surface termination. In some embodiments the substrate is pretreated with plasma.

Excess precursor and reaction byproducts, if any, are removed from the vicinity of the substrate, and in particular from the substrate surface, between precursor pulses. In some embodiments the reaction chamber is purged between precursor pulses, such as by purging with an inert gas. The flow rate and time of each precursor, is tunable, as is the removal step, allowing for control of the quality and various properties of the films.

As mentioned above, in some embodiments a gas is provided to the reaction chamber continuously during each deposition cycle, or during the entire ALD process, and reactive species are provided by generating a plasma in the gas, either in the reaction chamber or upstream of the reaction chamber. In some embodiments the plasma gas comprises nitrogen. In some embodiments the plasma gas is nitrogen. In other embodiments the plasma gas may comprise helium, hydrogen, or argon. In some embodiments the plasma gas is helium, hydrogen or argon. The plasma gas such us nitrogen, argon, helium or hydrogen may have a flow of 1 to 10, preferably 2 to 8, more preferably 3 to 6 and most preferably around 5 slm. The gas may also serve as a purge gas for the first and/or second precursor (or reactive species).

For example, flowing nitrogen may serve as a purge gas for a first silicon precursor and also serve as a second precursor (as a source of reactive species). In some embodiments, nitrogen, argon, or helium may serve as a purge gas for a first precursor and a source of excited species for converting the silicon precursor to the silicon nitride film. In some embodiments the gas in which the plasma is generated does not comprise argon and the adsorbed silicon precursor is not contacted with a reactive species generated by a plasma from Ar.

The cycle is repeated until a film of the desired thickness and composition is obtained. In some embodiments the deposition parameters, such as the flow rate, flow time, purge time, and/or precursors themselves, may be varied in one or more deposition cycles during the ALD process in order to obtain a film with the desired characteristics. In some embodiments, hydrogen and/or hydrogen plasma are not provided in a deposition cycle, or in the deposition process.

The term “pulse” may be understood to comprise feeding precursor into the reaction chamber for a predetermined amount of time. The term “pulse” does not restrict the length or duration of the pulse and a pulse can be any length of time.

In some embodiments, the silicon precursor is provided first. After an initial surface termination, if necessary or desired, a first silicon precursor pulse is supplied to the workpiece. In accordance with some embodiments, the first precursor pulse comprises a carrier gas flow and a volatile silicon halide species, such as H₂SiI₂, that is reactive with the workpiece surfaces of interest. Accordingly, the silicon precursor adsorbs upon these workpiece surfaces. The first precursor pulse self-saturates the workpiece surfaces such that any excess constituents of the first precursor pulse do not further react with the molecular layer formed by this process. The carrier gas may have a flow of 0.5 to 8, preferably 1 to 5, more preferably 2 to 3 and most preferably around 2.8 slm.

The first silicon precursor pulse is preferably supplied in gaseous form. The silicon precursor gas is considered “volatile” for purposes of the present description if the species exhibits sufficient vapor pressure under the process conditions to transport the species to the workpiece in sufficient concentration to saturate exposed surfaces.

In some embodiments the silicon precursor pulse is from about 0.05 seconds to about 5.0 seconds, about 0.1 seconds to about 3 seconds or about 0.2 seconds to about 1.0 seconds. The optimum pulsing time can be readily determined by the skilled artisan based on the particular circumstances.

In some embodiments the silicon precursor consumption rate is selected to provide a desired dose of precursor to the reaction space. precursor consumption refers to the amount of precursor consumed from the precursor source, such as a precursor source bottle, and can be determined by weighing the precursor source before and after a certain number of deposition cycles and dividing the mass difference by the number of cycles. In some embodiments the silicon precursor consumption is more than about 0.1 mg/cycle. In some embodiments the silicon precursor consumption is about 0.1 mg/cycle to about 50 mg/cycle, about 0.5 mg/cycle to about 30 mg/cycle or about 2 mg/cycle to about 20 mg/cycle. In some embodiments the minimum preferred silicon precursor consumption may be at least partly defined by the reactor dimensions, such as the heated surface area of the reactor. In some embodiments in a showerhead reactor designed for 300 mm silicon wafers, silicon precursor consumption is more than about 0.5 mg/cycle, or more than about 2.0 mg/cycle. In some embodiments the silicon precursor consumption is more than about 5 mg/cycle in a showerhead reactor designed for 300 mm silicon wafers. In some embodiments the silicon precursor consumption is more than about 1 mg/cycle, preferably more than 5 mg/cycle at reaction temperatures below about 400° C. in a showerhead reactor designed for 300 mm silicon wafers.

After sufficient time for a molecular layer to adsorb on the substrate surface, excess first silicon precursor is then removed from the reaction space. In some embodiments the excess first precursor is purged by stopping the flow of the first chemistry while continuing to flow a carrier gas or purge gas for a sufficient time to diffuse or purge excess precursors and reaction by-products, if any, from the reaction space. In some embodiments the excess first precursor is purged with the aid of inert gas, such as nitrogen or argon, that is flowing throughout the ALD cycle.

In some embodiments, the first precursor is purged for about 0.1 seconds to about 10 seconds, about 0.3 seconds to about 5 seconds or about 0.3 seconds to about 1 second. Provision and removal of the silicon precursor can be considered the first or silicon phase of the ALD cycle.

In the second phase, a second precursor comprising a reactive species, such as nitrogen plasma is provided to the workpiece. Nitrogen, N2, is flowed continuously to the reaction chamber during each ALD cycle in some embodiments. Nitrogen plasma may be formed by generating a plasma in nitrogen in the reaction chamber or upstream of the reaction chamber, for example by flowing the nitrogen through a remote plasma generator.

In some embodiments, plasma is generated in flowing H2 and N2 gases. In some embodiments the H2 and N2 are provided to the reaction chamber before the plasma is ignited or nitrogen and hydrogen atoms or radicals are formed. Without being bound to any theory, it is believed that the hydrogen may have a beneficial effect on the ligand removal step i.e. it may remove some of the remaining ligands or have other beneficial effects on the film quality. In some embodiments the H2 and N2 are provided to the reaction chamber continuously and nitrogen and hydrogen containing plasma, atoms or radicals is created or supplied when needed.

Typically, the second precursor, for example comprising nitrogen plasma, is provided for about 0.1 seconds to about 10 seconds. In some embodiments the second precursor, such as nitrogen plasma, is provided for about 0.1 seconds to about 10 seconds, 0.5 seconds to about 5 seconds or 0.5 seconds to about 2.0 seconds. However, depending on the reactor type, substrate type and its surface area, the second precursor pulsing time may be even higher than about 10 seconds. In some embodiments, pulsing times can be on the order of minutes. The optimum pulsing time can be readily determined by the skilled artisan based on the particular circumstances.

In some embodiments the second precursor is provided in two or more distinct pulses, without introducing another precursor in between any of the two or more pulses. For example, in some embodiments a nitrogen plasma is provided in two or more, preferably in two, sequential pulses, without introducing a Si-precursor in between the sequential pulses. In some embodiments during provision of nitrogen plasma two or more sequential plasma pulses are generated by providing a plasma discharge for a first period of time, extinguishing the plasma discharge for a second period of time, for example from about 0.1 seconds to about 10 seconds, from about 0.5 seconds to about 5 seconds or about 1.0 seconds to about 4.0 seconds, and exciting it again for a third period of time before introduction of another precursor or a removal step, such as before the Si-precursor or a purge step. Additional pulses of plasma can be introduced in the same way. In some embodiments a plasma is ignited for an equivalent period of time in each of the pulses.

Nitrogen plasma may be generated by applying RF power of from about 10 W to about 2000 W, preferably from about 50 W to about 1500 W, more preferably from about 100 W to about 800 W in some embodiments. In some embodiments the RF power density may be from about 0.02 W/cm² to about 2.0 W/cm², preferably from about 0.05 W/cm² to about 1.5 W/cm². The RF power may be applied to nitrogen that flows during the nitrogen plasma pulse time, that flows continuously through the reaction chamber, and/or that flows through a remote plasma generator. Thus in some embodiments the plasma is generated in situ, while in other embodiments the plasma is generated remotely. In some embodiments a showerhead reactor is utilized and plasma is generated between a substrate holder (on top of which the substrate is located) and a showerhead plate. In some embodiments the gap between the substrate holder and showerhead plate is from about 0.1 cm to about 20 cm, from about 0.5 cm to about 5 cm, or from about 0.8 cm to about 3.0 cm.

After a time period sufficient to completely saturate and react the previously adsorbed molecular layer with the nitrogen plasma pulse, any excess precursor and reaction byproducts are removed from the reaction space. As with the removal of the first precursor, this step may comprise stopping the generation of reactive species and continuing to flow the inert gas, such as nitrogen or argon for a time period sufficient for excess reactive species and volatile reaction by-products to diffuse out of and be purged from the reaction space. In other embodiments a separate purge gas may be used. The purge may, in some embodiments, be from about 0.1 seconds to about 10 seconds, about 0.1 seconds to about 4 seconds or about 0.1 seconds to about 0.5 seconds. Together, the nitrogen plasma provision and removal represent a second, reactive species phase in a silicon nitride atomic layer deposition cycle.

The two phases together represent one ALD cycle, which is repeated to form silicon nitride thin films of a desired thickness for the primary layer. While the ALD cycle is generally referred to herein as beginning with the silicon phase, it is contemplated that in other embodiments the cycle may begin with the reactive species phase. One of skill in the art will recognize that the first precursor phase generally reacts with the termination left by the last phase in the previous cycle. Thus, while no precursor may be previously adsorbed on the substrate surface or present in the reaction space if the reactive species phase is the first phase in the first ALD cycle, in subsequent cycles the reactive species phase will effectively follow the silicon phase. In some embodiments one or more different ALD cycles are provided in the deposition process.

According to some embodiments of the present disclosure, PEALD reactions may be performed at temperatures ranging from about 25° C. to about 700° C., preferably from about 50° C. to about 600° C., more preferably from about 100° C. to about 450° C., and most preferably from about 200° C. to about 400° C. In some embodiments, the optimum reactor temperature may be limited by the maximum allowed thermal budget. Therefore, in some embodiments the reaction temperature is from about 300° C. to about 400° C. In some applications, the maximum temperature is around about 400° C., and, therefore the PEALD process is run at that reaction temperature.

According to some embodiments of the present disclosure, the pressure of the reaction chamber during processing is maintained at from about 0.01 torr to about 50 torr, preferably from about 0.1 torr to about 10 torr.

Si Precursors

A number of suitable silicon halide precursors can be used in the presently disclosed PEALD processes. At least some of the suitable precursors may have the following general formula:

H_(2n+2−y−z)Si_(n)X_(y)A_(z)  (1)

wherein, n=1-10, y=1 or more (and up to 2n+2−z), z=0 or more (and up to 2n+2−y), X is I or Br, and A is a halogen other than X, preferably n=1-5 and more preferably n=1-3 and most preferably 1-2.

According to some embodiments, silicon halide precursors may comprise one or more cyclic compounds. Such precursors may have the following general formula:

H_(2n+2−y−z)Si_(n)X_(y)A_(z)  (2)

wherein the formula (2) compound is cyclic compound, n=3-10, y=1 or more (and up to 2n−z), z=0 or more (and up to 2n−y), X is I or Br, and A is a halogen other than X, preferably n=3-6.

According to some embodiments, silicon halide precursors may comprise one or more iodosilanes. Such precursors may have the following general formula:

H_(2n+2−y−z)Si_(n)I_(y)A_(z)  (3)

wherein, n=1-10, y=1 or more (and up to 2n+2−z), z=0 or more (and up to 2n+2−y), and A is a halogen other than I, preferably n=1-5 and more preferably n=1-3 and most preferably 1-2.

According to some embodiments, some silicon halide precursors may comprise one or more cyclic iodosilanes. Such precursors may have the following general formula:

H_(2n+2−y−z)Si_(n)I_(y)A_(z)  (4)

wherein the formula (4) compound is a cyclic compound, n=3-10, y=1 or more (and up to 2n−z), z=0 or more (and up to 2n−y), and A is a halogen other than I, preferably n=3-6.

According to some embodiments, some silicon halide precursors may comprise one or more bromosilanes. Such precursors may have the following general formula:

H_(2n+2−y−z)Si_(n)Br_(y)A_(z)  (5)

wherein, n=1-10, y=1 or more (and up to 2n+2−z), z=0 or more (and up to 2n+2−y), and A is a halogen other than Br, preferably n=1-5 and more preferably n=1-3 and most preferably 1-2.

According to some embodiments, some silicon halide precursors may comprise one or more cyclic bromosilanes. Such precursors may have the following general formula:

H_(2n+2−y−z)Si_(n)Br_(y)A_(z)  (6)

wherein the formula (6) compound is a cyclic compound, n=3-10, y=1 or more (and up to 2n−z), z=0 or more (and up to 2n−y), and A is a halogen other than Br, preferably n=3-6.

According to some embodiments, preferred silicon halide precursors comprise one or more iodosilanes. Such precursors may have the following general formula:

H_(2n+2−y−z)Si_(n)I_(y)  (7)

wherein, n=1-5, y=1 or more (up to 2n+2), preferably n=1-3 and more preferably n=1-2.

According to some embodiments, preferred silicon halide precursors comprise one or more bromosilanes. Such precursors may have the following general formula:

H_(2n+2−y−z)Si_(n)I_(y)  (8)

wherein, n=1-5, y=1 or more (up to 2n+2), preferably n=1-3 and more preferably n=1-2.

According to some embodiments of a PEALD process, suitable silicon halide precursors can include at least compounds having any one of the general formulas (1) through (8). In general formulas (1) through (8), halides/halogens can include F, Cl, Br and I. In some embodiments, a silicon halide precursor comprises SiI₄, HSiI₃, H₂SiI₂, H₃SiI, Si₂I₆, HSi₂I₅, H₂Si₂I₄, H₃Si₂I₃, H₄Si₂I₂, H₅Si₂I, or Si₃I₈. In some embodiments, a silicon precursor comprises one of HSiI₃, H₂SiI₂, H₃SiI, H₂Si₂I₄, H₄Si₂I₂, and H₅Si₂I. In some embodiments the silicon halide precursor comprises two, three, four, five or six of HSiI₃, H₂SiI₂, H₃SiI, H₂Si₂I₄, H₄Si₂I₂, and H₅Si₂I, including any combinations thereof.

In certain embodiments, the Si halide precursor is H₂SiI₂. In some embodiments, Si halide precursors of formulas (9)-(28), below, can be used in PEALD processes.

N Precursors

As discussed above, the second precursor according to the present disclosure may comprise a nitrogen precursor. In some embodiments the second precursor in a PEALD process may comprise a reactive species. Suitable plasma compositions include nitrogen plasma, radicals of nitrogen, or atomic nitrogen in one form or another. In some embodiments, the reactive species may comprise N-containing plasma or a plasma comprising N. In some embodiments, the reactive species may comprise a plasma comprising N-containing species. In some embodiments the reactive species may comprise nitrogen atoms and/or N* radicals. In some embodiments, hydrogen plasma, radicals of hydrogen, or atomic hydrogen in one form or another are also provided. And in some embodiments, a plasma may also contain noble gases, such as He, Ne, Ar, Kr and Xe, preferably Ar or He, in plasma form, as radicals, or in atomic form. In some embodiments, the second precursor does not comprise any species from a noble gas, such as Ar. Thus, in some embodiments plasma is not generated in a gas comprising a noble gas.

Thus, in some embodiments the second precursor may comprise plasma formed from compounds having both N and H, such as NH3 and N2H4, a mixture of N2/H2 or other precursors having an N—H bond. In some embodiments the second precursor may be formed, at least in part, from N2. In some embodiments the second precursor may be formed, at least in part, from N2 and H2, where the N2 and H2 are provided at a flow ratio (N2/H2) from about 20:1 to about 1:20, preferably from about 10:1 to about 1:10, more preferably from about 5:1 to about 1:5 and most preferably from about 1:2 to about 4:1, and in some cases 1:1.

The second precursor may be formed in some embodiments remotely via plasma discharge (“remote plasma”) away from the substrate or reaction space. In some embodiments, the second precursor may be formed in the vicinity of the substrate or directly above substrate (“direct plasma).

FIG. 1 is a flow chart generally illustrating a depositing a layer on a substrate in a reactor in accordance with some embodiments. According to certain embodiment, the process may comprise the following:

(1) a substrate comprising a three-dimensional structure is provided in a reaction space;

(2) a silicon halide precursor, such as SiI2H2, is introduced into the reaction space so that silicon-containing species are adsorbed to a surface of the substrate;

(3) excess silicon halide precursor and reaction byproducts are substantially removed from the reaction space;

(4) a nitrogen-containing precursor, such as N2, NH3, N2H4, or N2 and H2, is introduced into the reaction, and reactive species from the nitrogen precursor are created and the reactive species are contacted with the substrate; and

(5) removing excess nitrogen atoms, plasma, or radicals and reaction byproducts;

Steps (2) through (5) of the silicon nitride deposition cycle (7) may be repeated (6) until a silicon nitride film of a desired thickness is formed for the primary layer. The temperature of the substrate may be between 25 to 700° C. preferably from about 50° C. to about 600° C., more preferably from about 100° C. to about 550° C., and most preferably from about 200° C. to about 400° C. during providing a plasma gas and providing an energy source to create the plasma.

Nitrogen may flow continuously throughout the silicon nitride deposition cycle, with nitrogen plasma formed at the appropriate times to convert adsorbed silicon compound into silicon nitride.

As mentioned above, in some embodiments the substrate may be contacted simultaneously with the silicon compound and the reactive species to form the primary layer in a plasma enhanced chemical vapor deposition (PECVD) process.

The process may further comprise:

(8) stopping the introduction of the second precursor if the primary layer has reached a required thickness. The required thickness may be preset to a value of about 1 nm to about 50 nm, preferably from about 3 nm to about 30 nm, and more preferably from about 4 nm to about 15 nm. Subsequently, the silicon halide precursor may be introduced in the reactor at a temperature causing decomposition of the silicon halide precursor to provide a substantially pure amorphous silicon layer on top of the primary layer.

The substrate may be heated to a temperature between 400 to 900° C., preferably between 450 and 700° C., more preferably between 500 and 600° C., and even more preferable around 550° C. to decompose the silicon halide precursor in the reactor. The substantially pure amorphous silicon layer may be deposed at an increasing pressure when it is done without a plasma. The primary layer comprising silicon and the second precursor and the substantially pure amorphous silicon layer may have an improved etch rate when combined.

After stopping the introduction of the second precursor if the primary layer has reached a required thickness in (8) the silicon halide precursor may be introduced in the reactor at a temperature causing decomposition of the silicon halide precursor to provide a substantially pure amorphous silicon layer on top of the primary layer. During depositing the substantially pure amorphous silicon layer a nitrogen and oxygen poor plasma gas comprising helium, hydrogen and/or argon may be provided. An energy source may create a plasma from the plasma gas so to activate the silicon precursor. If a plasma is used the temperature may be lowered to between 20 to 400° C. preferably 100 to 300° C. during depositing the substantially pure silicon layer. The primary and substantially pure amorphous silicon layer may advantageously be provided in the same reactor chamber.

The layer comprising the primary layer comprising silicon and second precursor, and the substantially pure amorphous silicon layer on top may have an improved etch rate. The amorphous silicon may function as a skin or armor layer on top of the SiN layer for example to protect against an hydrogen fluoride (HF) etch.

The layer may be easily deposited because no different first precursor is required for the primary and substantially pure amorphous silicon layer. Further no different tool nor any transfer to a different reaction chamber may be necessary. The pure amorphous silicon layer may be selective to the primary layer such that it is only deposited on top of this layer. We can use the process to make Si rich SiN which will have high RI value and low WER. We can use it in combination with the temporal selectivity property of the silicon precursor because amorphous silicon may have a preferential growth on SiN.

According to some embodiments, a silicon nitride layer and an amorphous silicon layer on top is deposited using a plasma enhanced chemical vapor deposition PEALD process on a substrate having three-dimensional features, such as in a FinFET application. The features may have an aspect ratios of more than 2, preferably an aspect ratios of more than 3, more preferably an aspect ratios of more than 6 and most preferably an aspect ratios of more than 11. The process may comprise the steps as described above in conjunction with FIG. 1.

As described above the method may comprise depositing a pure amorphous silicon layer on top of a silicon nitride layer. The method may also be the other way around and comprising depositing a silicon nitride layer on top of a pure amorphous silicon layer creating a silicon layer with a silicon nitride crust resulting in a very high wet etch rate in tetramethylammonium hydroxide (TMAH).

The method may comprise depositing a silicon nitride layer on top of an amorphous layer on top of an silicon nitride layer on top of an amorphous layer in any ratio to create a multilayered cover. The multilayered cover allows to tune the stress, RI, etch properties of an SixNy layer system.

Thermal ALD Processes

The methods presented herein also allow deposition of silicon nitride films on substrate surfaces by thermal ALD processes. Geometrically challenging applications, such as 3-dimensional structures, are also possible with these thermal processes. According to some embodiments, thermal atomic layer deposition (ALD) type processes are used to form silicon nitride films on substrates such as integrated circuit workpieces.

A substrate or workpiece is placed in a reaction chamber and subjected to alternately repeated, self-limiting surface reactions. Preferably, for forming silicon nitride films each thermal ALD cycle comprises at least two distinct phases. The provision and removal of a precursor from the reaction space may be considered a phase. In a first phase, a first precursor comprising silicon is provided and forms no more than about one monolayer on the substrate surface. This precursor is also referred to herein as “the silicon precursor” or “silicon reactant” and may be, for example, a silicon halide such as H₂SiI₂. In a second phase, a second precursor comprising a nitrogen-containing compound is provided and reacts with the adsorbed silicon precursor to form SiN. This second precursor may also be referred to as a “nitrogen precursor” or “nitrogen reactant.” The second precursor may comprise NH₃ or another suitable nitrogen-containing compound. Additional phases may be added and phases may be removed as desired to adjust the composition of the final film.

One or more of the precursors may be provided with the aid of a carrier gas, such as Ar or He. In some embodiments the silicon precursor and the nitrogen precursor are provided with the aid of a carrier gas.

In some embodiments, two of the phases may overlap, or be combined. For example, the silicon precursor and the nitrogen precursor may be provided simultaneously in pulses that partially or completely overlap. In addition, although referred to as the first and second phases, and the first and second precursors, the order of the phases and the order of provision of precursors may be varied, and an ALD cycle may begin with any one of the phases or any of the precursors. That is, unless specified otherwise, the precursors can be provided in any order and the process may begin with any of the precursors.

As discussed in more detail below, in some embodiments for depositing a silicon nitride film, one or more deposition cycles typically begins with provision of the silicon precursor followed by the nitrogen precursor. In some embodiments, one or more deposition cycles begins with provision of the nitrogen precursor followed by the silicon precursor.

Again, one or more of the precursors may be provided with the aid of a carrier gas, such as Ar or He. In some embodiments the nitrogen precursor is provided with the aid of a carrier gas. In some embodiments, although referred to as a first phase and a second phase and a first and second precursor, the order of the phases and thus the order of provision of the precursors may be varied, and an ALD cycle may begin with any one of the phases.

In some embodiments the substrate on which deposition is desired, such as a semiconductor workpiece, is loaded into a reactor. The reactor may be part of a cluster tool in which a variety of different processes in the formation of an integrated circuit are carried out. In some embodiments a flow-type reactor is utilized. In some embodiments a shower head type of reactor is utilized. In some embodiments a space divided reactor is utilized. In some embodiments a high-volume manufacturing-capable single wafer ALD reactor is used. In other embodiments a batch reactor comprising multiple substrates is used. For embodiments in which batch ALD reactors are used, the number of substrates is preferably in the range of 10 to 200, more preferably in the range of 50 to 150, and most preferably in the range of 100 to 130.

Exemplary single wafer reactors, designed specifically to enhance ALD processes, are commercially available from ASM America, Inc. (Phoenix, Ariz.) under the tradenames Pulsar® 2000 and Pulsar® 3000 and ASM Japan K.K (Tokyo, Japan) under the tradename Eagle® XP, XP8 and Dragon®. Exemplary batch ALD reactors, designed specifically to enhance ALD processes, are commercially available from and ASM Europe B.V (Almere, Netherlands) under the tradenames A400™ and A412™.

In some embodiments, if necessary, the exposed surfaces of the workpiece can be pretreated to provide reactive sites to react with the first phase of the ALD process. In some embodiments a separate pretreatment step is not required. In some embodiments the substrate is pretreated to provide a desired surface termination.

In some embodiments, excess precursor and reaction byproducts, if any, are removed from the vicinity of the precursor, such as from the substrate surface, between precursor pulses. In some embodiments excess precursor and reaction byproducts are removed from the reaction chamber by purging between precursor pulses, for example with an inert gas. The flow rate and time of each precursor, is tunable, as is the purge step, allowing for control of the quality and properties of the films. In some embodiments removing excess precursor and/or reaction byproducts comprises moving the substrate.

As mentioned above, in some embodiments, a gas is provided to the reaction chamber continuously during each deposition cycle, or during the entire ALD process. In other embodiments the gas may be nitrogen, helium or argon.

The ALD cycle is repeated until a primary layer of the desired thickness and composition is obtained. In some embodiments the deposition parameters, such as the flow rate, flow time, purge time, and/or precursors themselves, may be varied in one or more deposition cycles during the ALD process in order to obtain a film with the desired characteristics.

The term “pulse” may be understood to comprise feeding precursor into the reaction chamber for a predetermined amount of time. The term “pulse” does not restrict the length or duration of the pulse and a pulse can be any length of time.

In some embodiments, the silicon precursor is provided first. After an initial surface termination, if necessary or desired, a first silicon precursor pulse is supplied to the workpiece. In accordance with some embodiments, the first precursor pulse comprises a carrier gas flow and a volatile silicon species, such as H₂SiI₂, that is reactive with the workpiece surfaces of interest. Accordingly, the silicon precursor adsorbs upon the workpiece surfaces. The first precursor pulse self-saturates the workpiece surfaces such that any excess constituents of the first precursor pulse do not substantially react further with the molecular layer formed by this process.

The first silicon precursor pulse is preferably supplied in gaseous form. The silicon precursor gas is considered “volatile” for purposes of the present description if the species exhibits sufficient vapor pressure under the process conditions to transport the species to the workpiece in sufficient concentration to saturate exposed surfaces.

In some embodiments the silicon precursor pulse is from about 0.05 seconds to about 5.0 seconds, about 0.1 seconds to about 3 seconds or about 0.2 seconds to about 1.0 second. In batch process the silicon precursor pulses can be substantially longer as can be determined by the skilled artisan given the particular circumstances.

After sufficient time for a molecular layer to adsorb on the substrate surface, excess first precursor is then removed from the reaction space. In some embodiments the excess first precursor is purged by stopping the flow of the first precursor while continuing to flow a carrier gas or purge gas for a sufficient time to diffuse or purge excess precursors and reaction by-products, if any, from the reaction space.

In some embodiments, the first precursor is purged for about 0.1 seconds to about 10 seconds, about 0.3 seconds to about 5 seconds or about 0.3 seconds to about 1 seconds. Provision and removal of the silicon precursor can be considered the first or silicon phase of the ALD cycle. In batch process the first precursor purge can be substantially longer as can be determined by the skilled artisan given the specific circumstances.

A second, nitrogen precursor is pulsed into the reaction space to contact the substrate surface. The nitrogen precursor may be provided with the aid of a carrier gas. The nitrogen precursor may be, for example, NH₃ or N₂H₄. The nitrogen precursor pulse is also preferably supplied in gaseous form. The nitrogen precursor is considered “volatile” for purposes of the present description if the species exhibits sufficient vapor pressure under the process conditions to transport the species to the workpiece in sufficient concentration to saturate exposed surfaces.

In some embodiments, the nitrogen precursor pulse is about 0.05 seconds to about 5.0 seconds, 0.1 seconds to about 3.0 seconds or about 0.2 seconds to about 1.0 second. In batch process the nitrogen precursor pulses can be substantially longer as can be determined by the skilled artisan given the specific circumstances.

After sufficient time for a molecular layer to adsorb on the substrate surface at the available binding sites, the second, nitrogen precursor is then removed from the reaction space. In some embodiments the flow of the second nitrogen precursor is stopped while continuing to flow a carrier gas for a sufficient time to diffuse or purge excess precursors and reaction by-products, if any, from the reaction space, preferably with greater than about two reaction chamber volumes of the purge gas, more preferably with greater than about three chamber volumes. Provision and removal of the nitrogen precursor can be considered the second or nitrogen phase of the ALD cycle.

In some embodiments, the nitrogen precursor is purged for about 0.1 seconds to about 10.0 seconds, about 0.3 seconds to about 5.0 seconds or about 0.3 seconds to about 1.0 second. In batch process the first precursor purge can be substantially longer as can be determined by the skilled artisan given the specific circumstances.

The flow rate and time of the nitrogen precursor pulse, as well as the removal or purge step of the nitrogen phase, are tunable to achieve a desired composition in the silicon nitride film. Although the adsorption of the nitrogen precursor on the substrate surface is typically self-limiting, due to the limited number of binding sites, pulsing parameters can be adjusted such that less than a monolayer of nitrogen is adsorbed in one or more cycles.

The two phases together represent one ALD cycle, which is repeated to form silicon nitrogen thin films of the desired thickness. While the ALD cycle is generally referred to herein as beginning with the silicon phase, it is contemplated that in other embodiments the cycle may begin with the nitrogen phase. One of skill in the art will recognize that the first precursor phase generally reacts with the termination left by the last phase in the previous cycle. In some embodiments one or more different ALD cycles are provided in the deposition process.

According to some embodiments of the present disclosure, ALD reactions may be performed at temperatures ranging from about 25° C. to about 1000° C., preferably from about 100° C. to about 800° C., more preferably from about 200° C. to about 650° C., and most preferably from about 300° C. to about 500° C. In some embodiments, the optimum reactor temperature may be limited by the maximum allowed thermal budget. Therefore, the reaction temperature can be from about 300° C. to about 400° C. In some applications, the maximum temperature is around about 400° C., and, therefore, the process is run at that reaction temperature.

Si Precursors

A number of suitable silicon precursors may be used in the presently disclosed processes. These silicon precursors may be used in thermal ALD processes. In some embodiments these precursors may also be used in plasma ALD or plasma CVD processes. In some embodiments these precursors may be introduced in the reactor at a temperature causing decomposition of the silicon halide precursor to provide a second substantially pure amorphous silicon layer on top of the primary layer thereby a layer with a desired quality (at least one of the desired WER, WERR, pattern loading effect or/and step coverage features described below) is deposited.

According to some embodiments, some silicon precursors comprise iodine and the film deposited by using that precursor has at least one desired property, for example at least one of the desired WER, WERR, pattern loading effect or/and step coverage features described below.

According to some embodiments, some silicon precursors comprise bromine and the film deposited by using that precursor have at least one desired property, for example at least one of the desired WER, WERR, pattern loading effect or/and step coverage features described below.

At least some of the suitable precursors may have the following general formula:

H_(2n+2−y−z−w)Si_(n)X_(y)A_(z)R_(w)  (9)

wherein, n=1-10, y=1 or more (and up to 2n+2−z−w), z=0 or more (and up to 2n+2−y−w), w=0 or more (and up to 2n+2−y−z), X is I or Br, A is a halogen other than X, R is an organic ligand and can be independently selected from the group consisting of alkoxides, alkylsilyls, alkyl, substituted alkyl, alkylamines and unsaturated hydrocarbon; preferably n=1-5 and more preferably n=1-3 and most preferably 1-2. Preferably R is a C₁-C₃ alkyl ligand, such as methyl, ethyl, n-propyl or isopropyl.

According to some embodiments, some silicon halide precursors comprise one or more cyclic compounds. Such precursors may have the following general formula:

H_(2n+2−y−z−w)Si_(n)I_(y)A_(z)R_(w)  (10)

wherein, n=3-10, y=1 or more (and up to 2n−z−w), z=0 or more (and up to 2n−y−w), w=0 or more (and up to 2n−y−z), X is I or Br, A is a halogen other than X, R is an organic ligand and can be independently selected from the group consisting of alkoxides, alkylsilyls, alkyl, substituted alkyl, alkylamines and unsaturated hydrocarbon; preferably n=3-6. Preferably R is a C1-C3 alkyl ligand, such as methyl, ethyl, n-propyl or isopropyl.

According to some embodiments, some silicon halide precursors comprise one or more iodosilanes. Such precursors may have the following general formula:

H_(2n−y−z−w)Si_(n)I_(y)A_(z)R_(w)  (11)

wherein, n=1-10, y=1 or more (and up to 2n+2−z−w), z=0 or more (and up to 2n+2−y−w), w=0 or more (and up to 2n+2−y−z), A is a halogen other than I, R is an organic ligand and can be independently selected from the group consisting of alkoxides, alkylsilyls, alkyl, substituted alkyl, alkylamines and unsaturated hydrocarbon; preferably n=1-5 and more preferably n=1-3 and most preferably 1-2. Preferably R is a C1-C3 alkyl ligand, such as methyl, ethyl, n-propyl or isopropyl.

According to some embodiments, some silicon halide precursors comprise one or more cyclic iodosilanes. Such precursors may have the following general formula:

H_(2n+2−y−z−w)Si_(n)I_(y)A_(z)R_(w)  (12)

wherein, n=3-10, y=1 or more (and up to 2n−z−w), z=0 or more (and up to 2n−y−w), w=0 or more (and up to 2n−y−z), A is a halogen other than I, R is an organic ligand and can be independently selected from the group consisting of alkoxides, alkylsilyls, alkyl, substituted alkyl, alkylamines and unsaturated hydrocarbon; preferably n=3-6. Preferably R is a C1-C3 alkyl ligand, such as methyl, ethyl, n-propyl or isopropyl.

According to some embodiments, some silicon halide precursors comprise one or more bromosilanes. Such precursors may have the following general formula:

H_(2n+2−y−z−w)Si_(n)Br_(y)A_(z)R_(w)  (13)

wherein, n=1-10, y=1 or more (and up to 2n+2−z−w), z=0 or more (and up to 2n+2−y−w), w=0 or more (and up to 2n+2−y−z), A is a halogen other than Br, R is an organic ligand and can be independently selected from the group consisting of alkoxides, alkylsilyls, alkyl, substituted alkyl, alkylamines and unsaturated hydrocarbon; preferably n=1-5 and more preferably n=1-3 and most preferably 1-2. Preferably R is a C1-C3 alkyl ligand, such as methyl, ethyl, n-propyl or isopropyl.

According to some embodiments, some silicon precursors comprise one or more cyclic bromosilanes. Such precursors may have the following general formula:

H_(2n−y−z−w)Si_(n)Br_(y)A_(z)R_(w)  (14)

wherein, n=3-10, y=1 or more (and up to 2n−z−w), z=0 or more (and up to 2n−y−w), w=0 or more (and up to 2n−y−z), A is a halogen other than Br, R is an organic ligand and can be independently selected from the group consisting of alkoxides, alkylsilyls, alkyl, substituted alkyl, alkylamines and unsaturated hydrocarbon; preferably n=3-6. Preferably R is a C1-C3 alkyl ligand such as methyl, ethyl, n-propyl or isopropyl.

According to some embodiments, some silicon precursors comprise one or more iodosilanes or bromosilanes in which the iodine or bromine is not bonded to the silicon in the compound. Accordingly some suitable compounds may have iodine/bromine substituted alkyl groups. Such precursors may have the following general formula:

H_(2n+2−y−z−w)Si_(n)X_(y)A_(z)R^(II) _(w)  (15)

wherein, n=1-10, y=0 or more (and up to 2n+2−z−w), z=0 or more (and up to 2n+2−y−w), w=1 or more (and up to 2n+2−y−z), X is I or Br, A is a halogen other than X, R^(II) is an organic ligand containing I or Br and can be independently selected from the group consisting of I or Br substituted alkoxides, alkylsilyls, alkyls, alkylamines and unsaturated hydrocarbons; preferably n=1-5 and more preferably n=1-3 and most preferably 1-2. Preferably R^(II) is an iodine substituted C₁-C₃ alkyl ligand.

According to some embodiments, some silicon precursors comprise one or more cyclic iodosilanes or bromosilanes. Accordingly some suitable cyclic compounds may have iodine/bromine substituted alkyl groups. Such precursors may have the following general formula:

H_(2n−y−z−w)Si_(n)X_(y)A_(z)R^(II) _(w)  (16)

wherein, n=3-10, y=0 or more (and up to 2n+2−z−w), z=0 or more (and up to 2n+2−y−w), w=1 or more (and up to 2n+2−y−z), X is I or Br, A is a halogen other than X, R^(II) is an organic ligand containing I or Br and can be independently selected from the group consisting of I or Br substituted alkoxides, alkylsilyls, alkyls, alkylamines and unsaturated hydrocarbons; preferably n=3-6. Preferably R is an iodine substituted C₁-C₃ alkyl ligand.

According to some embodiments, some suitable silicon precursors may have at least one of the following general formulas:

H_(2n+2−y−z−w)Si_(n)X_(y)A_(z)(NR₁R₂)_(w)  (17)

wherein, n=1-10, y=1 or more (and up to 2n+2−z−w), z=0 or more (and up to 2n+2−y−w), w=1 or more (and up to 2n+2−y−z), X is I or Br, A is a halogen other than X, N is nitrogen and R1 and R2 can be independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, silyl, alkylsilyl and unsaturated hydrocarbon; preferably n=1-5 and more preferably n=1-3 and most preferably 1-2. Preferably R₁ and R₂ are hydrogen or C₁-C₄ alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl, sec-butyl and n-butyl. More preferably R₁ and R₂ are hydrogen or C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl or isopropyl. Each of the (NR₁R₂)_(w) ligands can be independently selected from each other.

(H_(3−y−z−w)X_(y)A_(z)(NR₁R₂)_(w)Si)₃—N  (18)

wherein, y=1 or more (and up to 3−z−w), z=0 or more (and up to 3−y−w), w=1 or more (and up to 3−y−z), X is I or Br, A is a halogen other than X, N is nitrogen and R₁ and R₂ can be independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, silyl, alkylsilyl, and unsaturated hydrocarbon. Preferably R₁ and R₂ are hydrogen or C₁-C₄ alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl, sec-butyl and n-butyl. More preferably R₁ and R₂ are hydrogen or C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl or isopropyl. Each of the (NR₁R₂), ligands can be independently selected from each other. Each of the three H_(3−y−z−w)X_(y)A_(z)(NR₁R₂)_(w) Si ligands can be independently selected from each other.

In some embodiments, some suitable precursors may have at least one of the following more specific formulas:

H_(2n+2−y−w)Si_(n)I_(y)(NR₁R₂)_(w)  (19)

wherein, n=1-10, y=1 or more (and up to 2n+2−w), w=1 or more (and up to 2n+2−y), N is nitrogen, and R₁ and R₂ can be independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, silyl, alkylsilyl, and unsaturated hydrocarbon; preferably n=1-5 and more preferably n=1-3 and most preferably 1-2. Preferably R₁ and R₂ are hydrogen or C₁-C₄ alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl, sec-butyl and n-butyl. More preferably R₁ and R₂ are hydrogen or C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl or isopropyl. Each of the (NR₁R₂)_(w) ligands can be independently selected from each other.

(H_(3−y−w)I_(y)(NR₁R₂)_(w)Si)₃—N  (20)

wherein, y=1 or more (and up to 3−w), w=1 or more (and up to 3−y), N is nitrogen and R₁ and R₂ can be independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, silyl, alkylsilyl, and unsaturated hydrocarbon. Preferably R₁ and R₂ are hydrogen or C₁-C₄ alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl, sec-butyl and n-butyl. More preferably R₁ and R₂ are hydrogen or C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl or isopropyl. Each of the three H_(3−y−w)I_(y)(NR₁R₂)_(w)Si ligands can be independently selected from each other.

According to some embodiments, some suitable silicon precursors may have at least one of the following general formulas:

H_(2n+2−y−z−w)Si_(n)X_(y)A_(z)(NR₁R₂)_(w)  (21)

wherein, n=1-10, y=1 or more (and up to 2n+2−z−w), z=0 or more (and up to 2n+2−y−w), w=1 or more (and up to 2n+2−y−z), X is I or Br, A is a halogen other than X, N is nitrogen, R₁ can be independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, silyl, alkylsilyl, and unsaturated hydrocarbon, and R₂ can be independently selected from the group consisting of alkyl, substituted alkyl, silyl, alkylsilyl and unsaturated hydrocarbon; preferably n=1-5 and more preferably n=1-3 and most preferably 1-2. Preferably R₁ is hydrogen or C₁-C₄ alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl, sec-butyl, and n-butyl. More preferably R₁ is hydrogen or C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl, or isopropyl. Preferably R₂ is C₁-C₄ alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl, sec-butyl, and n-butyl. More preferably R₂ is C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl, or isopropyl. Each of the (NR₁R₂)_(w) ligands can be independently selected from each other.

(H_(3−y−z−w)X_(y)A_(z)(NR₁R₂)_(w)Si)₃—N  (22)

wherein, y=1 or more (and up to 3−z−w), z=0 or more (and up to 3−y−w), w=1 or more (and up to 3−y−z), X is I or Br, A is a halogen other than X, N is nitrogen, R₁ can be independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, silyl, alkylsilyl, and unsaturated hydrocarbon, and R₂ can be independently selected from the group consisting of alkyl, substituted alkyl, silyl, alkylsilyl, and unsaturated hydrocarbon; preferably n=1-5 and more preferably n=1-3 and most preferably 1-2. Preferably R₁ is hydrogen or C₁-C₄ alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl, sec-butyl, and n-butyl. More preferably R₁ is hydrogen or C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl, or isopropyl. Preferably R₂ is C₁-C₄ alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl, sec-butyl, and n-butyl. More preferably R₂ is C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl, or isopropyl. Each of the (NR₁R₂)_(w) ligands can be independently selected from each other.

In some embodiments, some suitable precursors may have at least one of the following more specific formulas:

H_(2n+2−y−w)Si_(n)I_(y)(NR₁R₂)_(w)  (23)

wherein, n=1-10, y=1 or more (and up to 2n+2−w), w=1 or more (and up to 2n+2−y), N is nitrogen, R₁ can be independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, silyl, alkylsilyl, and unsaturated hydrocarbon, and R₂ can be independently selected from the group consisting of alkyl, substituted alkyl, silyl, alkylsilyl, and unsaturated hydrocarbon; preferably n=1-5 and more preferably n=1-3 and most preferably 1-2. Preferably R₁ is hydrogen or C₁-C₄ alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl, sec-butyl, and n-butyl. More preferably R₁ is hydrogen or C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl, or isopropyl. Preferably R₂ is C₁-C₄ alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl, sec-butyl, and n-butyl. More preferably R₂ is C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl, or isopropyl. Each of the (NR₁R₂)_(w) ligands can be independently selected from each other.

(H_(3−y−w)I_(y)(NR₁R₂)_(w)Si)₃—N  (24)

wherein, y=1 or more (and up to 3−w), w=1 or more (and up to 3−y), N is nitrogen, R₁ can be independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, silyl, alkylsilyl, and unsaturated hydrocarbon, and R₂ can be independently selected from the group consisting of alkyl, substituted alkyl, silyl, alkylsilyl, and unsaturated hydrocarbon; preferably n=1-5 and more preferably n=1-3 and most preferably 1-2. Preferably R₁ is hydrogen or C₁-C₄ alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl, sec-butyl, and n-butyl. More preferably R₁ is hydrogen or C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl, or isopropyl. Preferably R₂ is C₁-C₄ alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl, sec-butyl, and n-butyl. More preferably R₂ is C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl, or isopropyl. Each of the (NR₁R₂)_(w) ligands can be independently selected from each other.

According to some embodiments of a thermal ALD process, suitable silicon halide precursors can include at least compounds having any one of the general formulas (9) through (24). In general formulas (9) through (18) as well as in general formulas (21) and (22), halides/halogens can include F, Cl, Br and I.

In some embodiments, a silicon precursor comprises one or more of the following: SiI₄, HSiI₃, H₂SiI₂, H₃SiI, Si₂I₆, HSi₂I₅, H₂Si₂I₄, H₃Si₂I₃, H₄Si₂I₂, H₅Si₂I, Si₃I₈, HSi₂I₅, H₂Si₂I₄, H₃Si₂I₃, H₄Si₂I₂, H₅Si₂I, MeSiI₃, Me₂SiI₂, Me₃SiI, MeSi₂I₅, Me₂Si₂I₄, Me₃Si₂I₃, Me₄Si₂I₂, Me₅Si₂I, HMeSiI₂, HMe₂SiI, HMeSi₂I₄, HMe₂Si₂I₃, HMe₃Si₂I₂, HMe₄Si₂I, H₂MeSiI, H₂MeSi₂I₃, H₂Me₂Si₂I₂, H₂Me₃Si₂I, H₃MeSi₂I₂, H₃Me₂Si₂I, H₄MeSi₂I, EtSiI₃, Et₂SiI₂, Et₃SiI, EtSi₂I₅, Et₂Si₂I₄, Et₃Si₂I₃, Et₄Si₂I₂, Et₅Si₂I, HEtSiI₂, HEt₂SiI HEtSi₂I₄, HEt₂Si₂I₃, HEt₃Si₂I₂, H₂EtSiI, H₂EtSi₂I₃, H₂Et₂Si₂I₂, H₂Et₃Si₂I, H₃EtSi₂I₂, H₃Et₂Si₂I, and H₄EtSi₂I.

In some embodiments, a silicon halide precursor comprises one or more of the following: EtMeSiI₂, Et₂MeSiI, EtMe₂SiI, EtMeSi₂I₄, Et₂MeSi₂I₃, EtMe₂Si₂I₃, Et₃MeSi₂I₂, Et₂Me₂Si₂I₂, EtMe₃Si₂I₂, Et₄MeSi₂I, Et₃Me₂Si₂I, Et₂Me₃Si₂I, EtMe₄Si₂I, HEtMeSiI, HetMeSi₂I₃, HEt₂MeSi₂I₂, HEtMe₂Si₂I₂, HEt₃MeSi₂I, HEt₂Me₂Si₂I, HEtMe₃Si₂I, H₂EtMeSi₂I₂, H₂Et₂MeSi₂I, H₂EtMe₂Si₂I, H₃EtMeSi₂I.

In some embodiments, a silicon halide precursor comprises one or more of the following: HSiI₃, H₂SiI₂, H₃SiI, H₂Si₂I₄, H₄Si₂I₂, H₅Si₂I, MeSiI₃, Me₂SiI₂, Me₃SiI, Me₂Si₂I₄, Me₄Si₂I₂, HMeSiI_(z), H₂Me₂Si₂I₂, EtSiI₃, Et₂SiI₂, Et₃SiI, Et₂Si₂I₄, Et₄Si₂I₂, and HEtSiI₂. In some embodiments a silicon precursor comprises two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen or more compounds selected from HSiI₃, H₂SiI₂, H₃SiI, H₂Si₂I₄, H₄Si₂I₂, H₅Si₂I, MeSiI₃, Me₂SiI₂, Me₃SiI, Me₂Si₂I₄, Me₄Si₂I₂, HMeSiI_(z), H₂Me₂Si₂I₂, EtSiI₃, Et₂SiI₂, Et₃SiI, Et₂Si₂I₄, Et₄Si₂I₂, and HEtSiI₂, including any combinations thereof. In certain embodiments, the silicon precursor is H₂SiI₂.

In some embodiments, a silicon halide precursor comprises three iodines and one amine or alkylamine ligands bonded to silicon. In some embodiments silicon halide precursor comprises one or more of the following: (SiI₃)NH₂, (SiI₃)NHMe, (SiI₃)NHEt, (SiI₃)NH^(i)Pr, (SiI₃)NH^(t)Bu, (SiI₃)NMe₂, (SiI₃)NMeEt, (SiI₃)NMe^(i)Pr, (SiI₃)NMe^(t)Bu, (SiI₃)NEt₂, (SiI₃)NEt^(i)Pr, (SiI₃)NEt^(t)Bu, (SiI₃)N^(i)Pr₂, (SiI₃)N^(i)Pr^(t)Bu, and (SiI₃)N^(t)Bu₂. In some embodiments, a silicon halide precursor comprises two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen or more compounds selected from (SiI₃)NH₂, (SiI₃)NHMe, (SiI₃)NHEt, (SiI₃)NH^(i)Pr, (SiI₃)NH^(t)Bu, (SiI₃)NMe₂, (SiI₃)NMeEt, (SiI₃)NMe^(i)Pr, (SiI₃)NMe^(t)Bu, (SiI₃)NEt₂, (SiI₃)NEt^(i)Pr, (SiI₃)NEt^(t)Bu, (SiI₃)N^(i)Pr₂, (SiI₃)N^(i)Pr^(t)Bu, (SiI₃)N^(t)Bu₂, and combinations thereof. In some embodiments, a silicon halide precursor comprises two iodines and two amine or alkylamine ligands bonded to silicon. In some embodiments, silicon halide precursor comprises one or more of the following: (SiI₂)(NH₂)₂, (SiI₂)(NHMe)₂, (SiI₂)(NHEt)₂, (SiI₂)(NH^(i)Pr)₂, (SiI₂)(NH^(t)Bu)₂, (SiI₂)(NMe₂)₂, (SiI₂)(NMeEt)₂, (SiI₂)(NMe^(i)Pr)₂, (SiI₂)(NMe^(t)Bu)₂, (SiI₂)(NEt₂)₂, (SiI₂)(NEt^(i)Pr)₂, (SiI₂)(NEt^(t)Bu)₂, (SiI₂)(N^(i)Pr₂)₂, (SiI₂)(N^(i)Pr^(t)Bu)₂, and (SiI₂)(N^(t)Bu)₂. In some embodiments, a silicon halide precursor comprises two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen or more compounds selected from (SiI₂)(NH₂)₂, (SiI₂)(NHMe)₂, (SiI₂)(NHEt)₂, (SiI₂)(NH^(i)Pr)₂, (SiI₂)(NH^(t)Bu)₂, (SiI₂)(NMe₂)₂, (SiI₂)(NMeEt)₂, (SiI₂)(NMe^(i)Pr)₂, (SiI2)(NMe^(t)Bu)₂, (SiI₂)(NEt₂)₂, (SiI₂)(NEt^(i)Pr)₂, (SiI₂)(NEt^(t)Bu)₂, (SiI₂)(N^(i)Pr)₂, (SiI₂)(N^(i)Pr^(t)Bu)₂, (SiI₂)(N^(t)Bu)₂, and combinations thereof.

In some embodiments, a silicon halide precursor comprises two iodines, one hydrogen and one amine or alkylamine ligand bonded to silicon. In some embodiments silicon halide precursor comprises one or more of the following: (SiI₂H)NH₂, (SiI₂H)NHMe, (SiI₂H)NHEt, (SiI₂H)NH^(i)Pr, (SiI₂H)NH^(t)Bu, (SiI₂H)NMe₂, (SiI₂H)NMeEt, (SiI₂H)NMe^(i)Pr, (SiI₂H)NMe^(t)Bu, (SiI₂H)NEt₂, (SiI₂H)NEt^(i)Pr, (SiI₂H)NEt^(t)Bu, (SiI₂H)N^(i)Pr₂, (SiI₂H)N^(i)P_(r) ^(t)Bu, and (SiI₂H)N^(t)Bu₂. In some embodiments a silicon halide precursor comprises two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen or more compounds selected from (SiI₂H)NH₂, (SiI₂H)NHMe, (SiI₂H)NHEt, (SiI₂H)NH^(i)Pr, (SiI₂H)NH^(t)Bu, (SiI₂H)NMe₂, (SiI₂H)NMeEt, (SiI₂H)NMe^(i)Pr, (SiI₂H)NMe^(t)Bu, (SiI₂H)NEt₂, (SiI₂H)NEt^(i)Pr, (SiI₂H)NEt^(t)Bu, (SiI₂H)N^(i)Pr₂, (SiI₂H)N^(i)Pr^(t)Bu, (SiI₂H)N^(t)Bu₂, and combinations thereof.

In some embodiments, a silicon halide precursor comprises one iodine, one hydrogen and two amine or alkylamine ligand bonded to silicon. In some embodiments, silicon halide precursor comprises one or more of the following: (SiIH)(NH₂)₂, (SiIH)(NHMe)₂, (SiIH)(NHEt)₂, (SiIH)(NH^(i)Pr)₂, (SiIH)(NH^(t)Bu)₂, (SiIH)(NMe₂)₂, (SiIH)(NHMe)₂, (SiIH)(NMe^(i)Pr)₂, (SiIH)(NMe^(t)Bu)₂, (SiIH)(NEt₂)₂, (SiIH)(NEt^(i)Pr)₂, (SiIH)(NEt^(t)Bu)₂, (SiIH)(N^(i)Pr₂)₂, (SiIH)(N^(i)Pr^(t)Bu)₂, and (SiIH)(N^(t)Bu)₂. In some embodiments, a silicon halide precursor comprises two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen or more compounds selected from (SiIH)(NH₂)₂, (SiIH)(NHMe)₂, (SiIH)(NHEt)₂, (SiIH)(NH^(i)Pr)₂, (SiIH)(NH^(t)Bu)₂, (SiIH)(NMe₂)₂, (SiIH)(NMeEt)₂, (SiIH)(NMe^(i)Pr)₂, (SiIH)(NMe^(t)Bu)₂, (SiIH)(NEt₂)₂, (SiIH)(NEt^(i)Pr)₂, (SiIH)(NEt^(t)Bu)₂, (SiIH)(N^(i)Pr₂)₂, (SiIH)(N^(i)Pr^(t)Bu)₂, and (SiIH)(N^(t)Bu)₂, and combinations thereof.

In some embodiments, a silicon halide precursor comprises one iodine, two hydrogens and one amine or alkylamine ligand bonded to silicon. In some embodiments silicon precursor comprises one or more of the following: (SiIH₂)NH₂, (SiIH₂)NHMe, (SiIH₂)NHEt, (SiIH₂)NH^(i)r, (SiIH₂)NH^(t)Bu, (SiIH₂)NMe₂, (SiIH₂)NMeEt, (SiIH₂)NMe^(i)Pr, (SiIH₂)NMe^(t)Bu, (SiIH₂)NEt₂, (SiIH₂)NEt^(i)Pr, (SiIH₂)NEt^(t)Bu, (SiIH₂)N^(i)Pr₂, (SiIH2)N^(i)Pr^(t)Bu, and (SiIH₂)N^(t)Bu₂. In some embodiments a silicon precursor comprises two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen or more compounds selected from (SiIH₂)NH₂, (SiIH₂)NHMe, (SiIH₂)NHEt, (SiIH₂)NH^(i)Pr, (SiIH₂)NH^(t)Bu, (SiIH₂)NMe₂, (SiIH₂)NMeEt, (SiIH₂)NMe^(i)Pr, (SiIH₂)NMe^(t)Bu, (SiIH₂)NEt₂, (SiIH₂)NEt^(i)Pr, (SiIH₂)NEt^(t)Bu, (SiIH₂)N^(i)Pr₂, (SiIH₂)N^(i)Pr^(t)Bu, (SiIH₂)N^(t)Bu₂, and combinations thereof.

In some embodiments, a silicon halide precursor comprises one iodine and three amine or alkylamine ligands bonded to silicon. In some embodiments, silicon precursor comprises one or more of the following: (SiI)(NH₂)₃, (SiI)(NHMe)₃, (SiI)(NHEt)₃, (SiI)(NH^(i)Pr)₃, (SiI)(NH^(t)Bu)₃, (SiI)(NMe₂)₃, (SiI)(NMeEt)₃, (SiI)(NMe^(i)Pr)₃, (SiI)(NMe^(t)Bu)₃, (SiI)(NEt₂)₃, (SiI)(NEt^(i)Pr)₃, (SiI)(NEt^(t)Bu)₃, (SiI)(N^(i)Pr₂)₃, (SiI)(N^(i)Pr^(t)Bu)₃, and (SiI)(N^(t)Bu)₃. In some embodiments a silicon precursor comprises two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen or more compounds selected from (SiI)(NH₂)₃, (SiI)(NHMe)₃, (SiI)(NHEt)³, (SiI)(NH^(i)Pr)₃, (SiI)(NH^(t)Bu)₃, (SiI)(NMe₂)₃, (SiI)(NMeEt)₃, (SiI)(NMe^(i)Pr)₃, (SiI)(NMe^(t)Bu)₃, (SiI)(NEt₂)₃, (SiI)(NEt^(i)Pr)₃, (SiI)(NEt^(t)Bu)₃, (SiI)(N^(i)Pr₂)₃, (SiI)(N^(i)Pr^(t)Bu)₃, (SiI)(N^(t)Bu)₃, and combinations thereof.

In certain embodiments, a silicon halide precursor comprises two iodines, hydrogen and one amine or alkylamine ligand or two iodines and two alkylamine ligands bonded to silicon and wherein amine or alkylamine ligands are selected from amine NH₂—, methylamine MeNH—, dimethylamine Me₂N—, ethylmethylamine EtMeN—, ethylamine EtNH—, and diethylamine Et₂N—. In some embodiments silicon halide precursor comprises one or more of the following: (SiI₂H)NH₂, (SiI₂H)NHMe, (SiI₂H)NHEt, (SiI₂H)NMe₂, (SiI₂H)NMeEt, (SiI₂H)NEt₂, (SiI₂)(NH₂)₂, (SiI₂)(NHMe)₂, (SiI₂)(NHEt)₂, (SiI₂)(NMe₂)₂, (SiI₂)(NMeEt)₂, and (SiI₂)(NEt₂)₂. In some embodiments a silicon precursor comprises two, three, four, five, six, seven, eight, nine, ten, eleven, twelve or more compounds selected from (SiI₂H)NH₂, (SiI₂H)NHMe, (SiI₂H)NHEt, (SiI₂H)NMe₂, (SiI₂H)NMeEt, (SiI₂H)NEt₂, (SiI₂)(NH₂)₂, (SiI₂)(NHMe)₂, (SiI₂)(NHEt)₂, (SiI₂)(NMe₂)₂, (SiI₂)(NMeEt)₂, (SiI₂)(NEt₂)₂, and combinations thereof.

Other Types of Si-Precursors Containing I or Br

A number of suitable silicon halide precursors containing nitrogen, such as iodine or bromine substituted silazanes, or sulphur, may be used in the presently disclosed thermal and plasma ALD processes. In some embodiments silicon precursors containing nitrogen, such as iodine or bromine substituted silazanes, may be used in the presently disclosed thermal and plasma ALD processes in which a film with desired quality is to be deposited, for example at least one of the desired WER, WERR, pattern loading effect or/and step coverage features described below.

At least some of the suitable iodine or bromine substituted silicon halide precursors may have the following general formula:

H_(2n+2−y−z−w)Si_(n)(EH)_(n-1)X_(y)A_(z)R_(w)  (25)

wherein, n=2-10, y=1 or more (and up to 2n+2−z−w), z=0 or more (and up to 2n+2−y−w), w=0 or more (and up to 2n+2−y−z), X is I or Br, E is N or S, preferably N, A is a halogen other than X, R is an organic ligand and can be independently selected from the group consisting of alkoxides, alkylsilyls, alkyl, substituted alkyl, alkylamines and unsaturated hydrocarbon; preferably n=2-5 and more preferably n=2-3 and most preferably 1-2. Preferably R is a C₁-C₃ alkyl ligand, such as methyl, ethyl, n-propyl or isopropyl.

At least some of the suitable iodine or bromine substituted silazane precursors may have the following general formula:

H_(2n+2−y−z−w)Si_(n)(NH)_(n-1)X_(y)A_(z)R_(w)  (26)

wherein, n=2-10, y=1 or more (and up to 2n+2−z−w), z=0 or more (and up to 2n+2−y−w), w=0 or more (and up to 2n+2−y−z), X is I or Br, A is a halogen other than X, R is an organic ligand and can be independently selected from the group consisting of alkoxides, alkylsilyls, alkyl, substituted alkyl, alkylamines and unsaturated hydrocarbon; preferably n=2-5 and more preferably n=2-3 and most preferably 2. Preferably R is a C₁-C₃ alkyl ligand, such as methyl, ethyl, n-propyl or isopropyl.

In some embodiments, the silicon halide precursor comprises Si-compound, such as heterocyclic Si compound, which comprises I or Br. Such cyclic precursors may comprise the following substructure:

—Si-E-Si—  (27)

wherein E is N or S, preferably N.

In some embodiments the silicon halide precursor comprises substructure according to formula (27) and example of this kind of compounds is for example, iodine or bromine substituted cyclosilazanes, such iodine or bromine substituted cyclotrisilazane.

In some embodiments, the silicon halide precursor comprises Si-compound, such as silylamine based compound, which comprises I or Br. Such silylamine based Si-precursors may have the following general formula:

(H_(3−y−z−w)X_(y)A_(z)R_(w)Si)₃—N  (28)

wherein, y=1 or more (and up to 3−z−w), z=0 or more (and up to 3−y−w), w=0 or more (and up to 3−y−z), X is I or Br, A is a halogen other than X, R is an organic ligand and can be independently selected from the group consisting of alkoxides, alkylsilyls, alkyl, substituted alkyl, alkylamines and unsaturated hydrocarbon. Preferably R is a C₁-C₃ alkyl ligand, such as methyl, ethyl, n-propyl or isopropyl. Each of the three H_(3−y−z−w)X_(y)A_(z)R_(w)Si ligands can be independently selected from each other.

N Precursors

A number of suitable second precursors may be used in the presently disclosed processes. These second precursors may be used in thermal ALD processes. In some embodiments these precursors may also be used in plasma ALD or plasma CVD processes thereby a layer with a desired quality (at least one of the desired WER, WERR, pattern loading effect or/and step coverage features described below) is deposited.

According to some embodiments, the second precursor or nitrogen precursor in a thermal ALD process may be NH₃, N₂H₄, or any number of other suitable nitrogen compounds having a N—H bond.

SiN Film Characteristics

The silicon nitride thin films deposited according to some of the embodiments discussed herein (irrespective of whether the silicon precursor contained bromine or iodine) may achieve impurity levels or concentrations below about 3%, preferably below about 1%, more preferably below about 0.5%, and most preferably below about 0.1%. In some thin films, the total impurity level excluding hydrogen may be below about 5%, preferably below about 2%, more preferably below about 1%, and most preferably below about 0.2%. And in some thin films, hydrogen levels may be below about 30%, preferably below about 20%, more preferably below about 15%, and most preferably below about 10%.

In some embodiments, the deposited SiN films do not comprise an appreciable amount of carbon. However, in some embodiments a SiN film comprising carbon is deposited. For example, in some embodiments an ALD reaction is carried out using a silicon precursor comprising carbon and a thin silicon nitride film comprising carbon is deposited. In some embodiments a SiN film comprising carbon is deposited using a precursor comprising an alkyl group or other carbon-containing ligand. In some embodiments a silicon precursor of one of formulas (9)-(28) and comprising an alkyl group is used in a PEALD or thermal ALD process, as described above, to deposit a SiN film comprising carbon. Different alkyl groups, such as Me or Et, or other carbon-containing ligands may produce different carbon concentrations in the films because of different reaction mechanisms. Thus, different precursors can be selected to produce different carbon concentration in deposited SiN films. In some embodiments the thin SiN film comprising carbon may be used, for example, as a low-k spacer. In some embodiments the thin films do not comprise argon.

According to some embodiments, the silicon nitride thin films may exhibit step coverage and pattern loading effects of greater than about 50%, preferably greater than about 80%, more preferably greater than about 90%, and most preferably greater than about 95%. In some cases step coverage and pattern loading effects can be greater than about 98% and in some case about 100% (within the accuracy of the measurement tool or method). These values can be achieved in aspect ratios of more than 2, preferably in aspect ratios more than 3, more preferably in aspect ratios more than 6 and most preferably in aspect ratios more than 11.

As used herein, “pattern loading effect” is used in accordance with its ordinary meaning in this field. While pattern loading effects may be seen with respect to impurity content, density, electrical properties and etch rate, unless indicated otherwise the term pattern loading effect when used herein refers to the variation in film thickness in an area of the substrate where structures are present. Thus, the pattern loading effect can be given as the film thickness in the sidewall or bottom of a feature inside a three-dimensional structure relative to the film thickness on the sidewall or bottom of the three-dimensional structure/feature facing the open field. As used herein, a 100% pattern loading effect (or a ratio of 1) would represent about a completely uniform film property throughout the substrate regardless of features i.e. in other words there is no pattern loading effect (variance in a particular film property, such as thickness, in features vs. open field).

In some embodiments, silicon nitride films are deposited to a thicknesses of from about 1 nm to about 50 nm, preferably from about 3 nm to about 30 nm, more preferably from about 4 nm to about 15 nm. These thicknesses can be achieved in feature sizes (width) below about 100 nm, preferably about 50 nm, more preferably below about 30 nm, most preferably below about 20 nm, and in some cases below about 15 nm. According to some embodiments, a SiN film is deposited on a three-dimensional structure and the thickness at a sidewall may be around 10 nm.

It has been found that in using the silicon nitride thin films of the present disclosure, thickness differences between top and side may not be as critical for some applications, due to the improved film quality and etch characteristics. Nevertheless, in some embodiments, the thickness gradient along the sidewall may be very important to subsequent applications or processes.

Amorphous Silicon Layer Characteristics

The substantially pure amorphous silicon (A-Si) layer deposited according to some of the embodiments discussed herein (irrespective of whether the silicon precursor contained bromine or iodine) may achieve impurity levels or concentrations below about 3%, preferably below about 1%, more preferably below about 0.5%, and most preferably below about 0.1%. In some thin films, the total impurity level excluding hydrogen may be below about 5%, preferably below about 2%, more preferably below about 1%, and most preferably below about 0.2%. And in some thin films, hydrogen levels may be below about 30%, preferably below about 20%, more preferably below about 15%, and most preferably below about 10%.

In some embodiments, the deposited A-Si layer do not comprise an appreciable amount of carbon. However, in some embodiments an A-Si layer comprising carbon is deposited. For example, in some embodiments an ALD reaction is carried out using a silicon precursor comprising carbon and a thin A-Si layer comprising carbon is deposited. In some embodiments a A-Si layer comprising carbon is deposited using a precursor comprising an alkyl group or other carbon-containing ligand. In some embodiments a silicon precursor of one of formulas (9)-(28) and comprising an alkyl group is used in a PEALD, PECVD or thermal CVD process, as described above, to deposit a A-Si film comprising carbon. In some embodiments the thin SiN film comprising carbon may be used, for example, as a low-k spacer.

According to some embodiments, the A-Si films may exhibit step coverage and pattern loading effects of greater than about 50%, preferably greater than about 80%, more preferably greater than about 90%, and most preferably greater than about 95%. In some cases step coverage and pattern loading effects can be greater than about 98% and in some case about 100% (within the accuracy of the measurement tool or method). These values can be achieved in aspect ratios of more than 2, preferably in aspect ratios more than 3, more preferably in aspect ratios more than 6 and most preferably in aspect ratios more than 11.

As used herein, “pattern loading effect” is used in accordance with its ordinary meaning in this field. While pattern loading effects may be seen with respect to impurity content, density, electrical properties and etch rate, unless indicated otherwise the term pattern loading effect when used herein refers to the variation in film thickness in an area of the substrate where structures are present. Thus, the pattern loading effect can be given as the film thickness in the sidewall or bottom of a feature inside a three-dimensional structure relative to the film thickness on the sidewall or bottom of the three-dimensional structure/feature facing the open field. As used herein, a 100% pattern loading effect (or a ratio of 1) would represent about a completely uniform film property throughout the substrate regardless of features i.e. in other words there is no pattern loading effect (variance in a particular film property, such as thickness, in features vs. open field).

In some embodiments, amorphous silicon A-Si films are deposited to a thicknesses of from about 0.1 nm to about 40 nm, preferably from about 1 nm to about 20 nm, more preferably from about 1.5 nm to about 5 nm. These thicknesses can be achieved in feature sizes (width) below about 100 nm, preferably about 50 nm, more preferably below about 30 nm, most preferably below about 20 nm, and in some cases below about 15 nm. According to some embodiments, a A-Si film is deposited on a three-dimensional structure and the thickness at a sidewall may be slightly even more than 10 nm.

Specific Contexts for Use of SiN/A-Si Films

The methods and materials described herein can provide films with increased quality and improved etch properties not only for traditional lateral transistor designs, with horizontal source/drain (S/D) and gate surfaces, but can also provide improved SiN/A-Si films for use on non-horizontal (e.g., vertical) surfaces, and on complex three-dimensional (3D) structures. In certain embodiments, SiN/A-Si films are deposited by the disclosed methods on a three-dimensional structure during integrated circuit fabrication. The three-dimensional transistor may include, for example, double-gate field effect transistors (DG FET), and other types of multiple gate FETs, including FinFETs. For example, the silicon nitride/amorphous silicon thin films of the present disclosure may be useful in nonplanar multiple gate transistors, such as FinFETs, where it may be desirable to form silicide on vertical walls, in addition to the tops of the gate, source, and drain regions.

Example 1

A primary 7 nm silicon nitride thin layer was deposited at 550° C. according to the present disclosure by a PEALD process using H2SiI2 as the first (silicon) precursor and H2+N2 plasma gas as the second (nitrogen) precursor on a first and second bare Si-substrate (wafer) with native oxide. The second substrate additionally received a second amorphous silicon layer by constantly flowing H2SiI2 at 550° C. for 5 minutes.

The thickness of the layers on the substrates were measured with a spectroscopic ellipsometer. The second substrate has a 2 nm thicker layer (THK). Substrate 1 and 2 were submitted to a 1.5% hydrogenfluoride etch for four minutes. Again the substrates were measured:

TABLE 1 7 nm 2 nm thk NU % 4 min HF thk NU % WER wafer SiN depo a-Si depo as depo as depo 1.5% dip post etch post etch (nm/min) 1 x 8.5 0.8 x 4.2 6.9 1.1 2 x x 10.6 1.2 x 10 3.3 0.2

The second substrate (Wafer 2) shows significantly (±7 times) lower WERR than wafer 1, wafer 2 also show better uniformity (NU) after etch indicating that the amorphous silicon layer improves the etch resistance of the layer significantly in table 1. The amorphous silicon layer Si layer may be oxidize or nitrated after etch as desired.

Example 2

FIGS. 2a and 2b show images from layers deposited according to an embodiment on some high aspect ratio structures. FIG. 2a depicts a primary layer of silicon nitride SiN with a second amorphous silicon layer A-Si. In between there may be a very thin interfacial layer (INT) of unknown composition. FIG. 2b depicts an identical layer after hydrogenfluoride HF 1.5% etch for four minutes.

FIG. 2b shows no significant etching indicating that the amorphous silicon layer improves the etch resistance of the layer significantly. It can be seen that both a-Si and SiN depo are smooth and conformal.

It will be understood by those of skill in the art that numerous and various modifications can be made without departing from the spirit of the present invention. The described features, structures, characteristics and precursors can be combined in any suitable manner. Therefore, it should be clearly understood that the forms of the present invention are illustrative only and are not intended to limit the scope of the present invention. All modifications and changes are intended to fall within the scope of the invention, as defined by the appended claims.

It is to be understood that the configurations and/or approaches described herein are exemplary in nature, and that these specific embodiments or examples are not to be considered in a limiting sense, because numerous variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. Thus, the various acts illustrated may be performed in the sequence illustrated, in other sequences, or omitted in some cases. 

What is claimed is:
 1. A method of providing a structure by depositing a layer on a substrate in a reactor; the method comprising: introducing a first precursor comprising a silicon halide in the reactor; introducing a second precursor in the reactor; providing an energy source to create a plasma from the second precursor so that the second precursor reacts with the first precursor until a primary layer comprising silicon and second precursor of a desired thickness is formed; subsequently introducing the silicon halide in the reactor at a temperature causing decomposition of the silicon halide precursor to provide a substantially pure amorphous silicon layer on top of the primary layer.
 2. A method of providing a structure by depositing a layer on a substrate in a reactor, the method comprising: introducing a first precursor comprising silicon halide in the reactor at a temperature causing decomposition of the silicon halide precursor to provide a substantially pure amorphous silicon, introducing a second precursor in the reactor; and, providing an energy source to create a plasma from the second precursor so that the second precursor reacts with the first precursor until a primary layer comprising silicon and second precursor of a desired thickness is formed.
 3. The method according to claim 1, wherein the second precursor comprises nitrogen and the primary layer comprises silicon nitride.
 4. The method according to claim 1, wherein the second precursor comprises oxygen and the primary layer comprises silicon dioxide
 5. The method according to claim 1, wherein the method comprises bringing the temperature of the substrate to between 25 to 700° C. during introducing the second precursor and providing an energy source to create a plasma.
 6. The method according to claim 1, wherein the method comprises heating the substrate to a temperature between 350 to 900° C. to decompose the silicon halide in the reactor space.
 7. The method according to claim 1, wherein introducing a silicon halide in the reactor comprises adsorbing the silicon halide to a surface of the substrate.
 8. The method according to claim 7, wherein the deposition method also comprises after the plasma is created contacting adsorbed silicon halide with second precursor species of the plasma.
 9. The method according to claim 1, wherein the method is a plasma enhanced atomic layer deposition method and the deposition method comprises removing excess first precursor and reaction byproducts from the reactor space after introducing the first precursor; and, after providing an energy source to create a plasma from the second precursor.
 10. The method according to claim 1, wherein the method to form the primary layer is a plasma enhanced atomic layer deposition method and the deposition method comprises removing excess first precursor and reaction byproducts from the reactor space after introducing the first precursor; and, after providing an energy source to create a plasma from the second precursor.
 11. The method according to claim 1, wherein the method to form the primary layer is a plasma enhanced chemical vapor deposition method.
 12. The method according to claim 1, wherein the substantially pure amorphous silicon layer is formed at a temperature below the decomposition temperature, using a PECVD deposition method providing an energy source to create a plasma from a gas mixture comprising the silicon precursor and substantially free of oxygen and nitrogen until a substantially pure amorphous silicon layer of a desired thickness is formed.
 13. The method according to claim 1, wherein the method to form the substantially pure amorphous layer is a plasma enhanced atomic layer deposition method and the deposition method comprises removing excess silicon precursor and reaction byproducts from the reactor space after introducing the silicon precursor; and, after providing an energy source to create a plasma from a gas mixture substantially free of oxygen and nitrogen to form the substantially pure amorphous layer.
 14. The method of claim 1, wherein the layers are deposited on a structure with an aspect ratio of at least 1:3.
 15. The method according to claim 14, wherein the structure will form a semiconductor logic or memory device, preferably a FinFET.
 16. The method according to claim 1, wherein the silicon halide precursor comprises a halogen selected from the group comprising fluorine, chlorine, iodine and bromine.
 17. The method according to claim 1, wherein introducing a vapor-phase silicon precursor in the reactor space is accomplished using a carrier gas.
 18. The method according to claim 17, wherein the carrier gas comprises a nitrogen carrier gas with a flow of 0.5 to 8 slm.
 19. The method according to claim 17, wherein the carrier gas comprises an argon carrier gas with a flow of 0.5 to 8 slue.
 20. The method according to claim 1, wherein the pressure in the reactor is between 0.01 torr to 50 torr.
 21. The method according to claim 1, wherein the plasma is created with an energy source having a power between 50 and 1500 Watt.
 22. The method according to claim 1, wherein the second precursor is introduced with a carrier gas comprising argon, helium or hydrogen with a flow of 1 to 10 slm.
 23. The method according to claim 12, wherein the gas mixture used for the plasma comprises argon, helium or hydrogen introduced with a flow of 1 to 10 slm.
 24. The method according to claim 1 wherein the substantially pure amorphous silicon layer on top of the primary layer changes the etch properties of the primary layer to the etch properties of the substantially pure amorphous silicon layer.
 25. The method according to claim 2 wherein the primary layer on top of the substantially pure amorphous silicon layer changes the etch properties of the substantially pure amorphous silicon layer to the etch properties of the primary layer.
 26. The method according to claim 1, wherein the substantially pure amorphous silicon layer is less than 10 nm thick.
 27. The method according to claim 1, wherein the primary and substantially pure amorphous silicon layer are provided in the same reactor chamber.
 28. The method according to claim 1, wherein depositing the substantially pure amorphous silicon layer comprises increasing the pressure and/or temperature.
 29. The method according to claim 2 wherein the second precursor comprises oxygen and a primary layer comprising silicon dioxide is formed on top of the substantially pure amorphous silicon layer so that the amorphous silicon layer act as an oxidation protection layer for the underlying layer.
 30. The method according to claim 29, wherein a part of the substantially pure amorphous silicon layer is converted to silicon dioxide during the deposition of the primary layer comprising silicon dioxide.
 31. The method according to claim 1, wherein a nanolaminate of silicon/silicon dioxide/silicon nitride is formed in any ratio or order until the nanolaminate layer reaches the desired thickness.
 32. The method according to claim 31 wherein the properties (WER, DER, stress, RI) have been tuned by adjusting the ratio and order of the silicon/silicon dioxide/silicon nitride nanolaminate layer. 